KR20230066549A - Polyamide, molded article and film made of the same, and method for producing the polyamide - Google Patents

Abstract

The present invention provides a polyamide and a polyamide film more sufficiently excellent in all of heat resistance, flexibility and rubber elasticity. The present invention provides a unit composed of a C18 or more aliphatic dicarboxylic acid (A), a C18 or more aliphatic diamine (B), a C12 or less aromatic dicarboxylic acid (C), and a C12 or less A polyamide containing a unit consisting of an aliphatic diamine (D) of 240 ° C. or more, a crystal fusion enthalpy of 20 J / g or more, and an elongation recovery rate in a hysteresis test of 50% or more, and containing the polyamide It is about polyamide film.

Description

Polyamide, molded article and film made of the same, and method for producing the polyamide

The present invention relates to a polyamide excellent in heat resistance, flexibility, and rubber elasticity, a molded article and a film made therefrom, and a method for producing the polyamide.

Polyamide having high flexibility and rubber elasticity is widely used for tubes and hoses, daily necessities shoes, sealing materials, and the like. Such a polyamide usually contains a polyether component or a polyester component in order to impart flexibility and rubber elasticity. In recent years, applications of such polyamides to automobile parts, peripheral parts of electronic devices, and battery materials have been studied, and high heat resistance is further required for polyamides used in the above fields.

In order to obtain a polyamide with high heat resistance, it is necessary to increase the polymerization temperature. When the polymerization temperature is increased, there is a problem that the molecular weight is lowered because the polyether component or polyester component used for imparting flexibility is decomposed, and the performance is further insufficient.

As a polyamide that does not use a polyether component or a polyester component, Patent Document 1 discloses a polyamide composed of terephthalic acid, 1,10-decanediamine, dimer acid, and dimer diamine. Patent Document 2 discloses a polyamide composed of adipic acid, 1,4-butylenediamine, dimer acid, and dimer diamine.

International Publication No. 2020/085360 pamphlet Japanese Patent Publication No. 2014-506614

However, the polyamides of Patent Literature 1 and Patent Literature 2 had a problem that, although heat resistance was improved, flexibility and rubber elasticity were not sufficiently improved.

The present invention is to solve the above problems, and an object of the present invention is to provide a polyamide more sufficiently excellent in all of heat resistance, flexibility and rubber elasticity.

The present inventors obtained a reaction product by reacting an aromatic dicarboxylic acid (C) having 12 or less carbon atoms with an aliphatic diamine (D) having 12 or less carbon atoms, and then obtained the reaction product with an aliphatic dicarboxylic acid (A) having 18 or more carbon atoms and 18 carbon atoms. It was discovered that the above object could be achieved by reacting with the above aliphatic diamine (B) to polymerize, and reached the present invention.

That is, the gist of the present invention is as follows.

(1) A unit composed of an aliphatic dicarboxylic acid (A) having 18 or more carbon atoms, a unit composed of an aliphatic diamine (B) having 18 or more carbon atoms, a unit composed of an aromatic dicarboxylic acid (C) having 12 or less carbon atoms, and a unit composed of a C 12 or less aliphatic dicarboxylic acid (C) A polyamide containing a unit composed of an aliphatic diamine (D), having a melting point of 240°C or higher, a crystal fusion enthalpy of 20 J/g or higher, and an elongation recovery rate of 50% or higher in a hysteresis test.

(2) The polyamide according to (1), wherein the C18 or more aliphatic dicarboxylic acid (A) is a dimer acid.

(3) The polyamide according to (1) or (2), wherein the aliphatic diamine (B) having 18 or more carbon atoms is a dimer diamine.

(4) The polyamide according to any one of (1) to (3), wherein the aromatic dicarboxylic acid (C) having 12 or less carbon atoms is terephthalic acid.

(5) The polyamide according to any one of (1) to (4), wherein the C12 or less aliphatic diamine (D) is 1,10-decanediamine.

(6) The total content of the unit composed of an aliphatic dicarboxylic acid (A) having 18 or more carbon atoms and the unit composed of an aliphatic diamine (B) having 18 or more carbon atoms is 10 to 90 with respect to all the monomer components constituting the polyamide. The polyamide according to any one of (1) to (5), which is % by mass.

(7) The total content of the unit composed of an aliphatic dicarboxylic acid (A) having 18 or more carbon atoms and the unit composed of an aliphatic diamine (B) having 18 or more carbon atoms is 20 to 80 with respect to all the monomer components constituting the polyamide. The polyamide according to any one of (1) to (6), which is % by mass.

(8) The number of carbon atoms of the aliphatic dicarboxylic acid (A) having 18 or more carbon atoms is 30 to 40,

The number of carbon atoms of the aliphatic diamine (B) having 18 or more carbon atoms is 30 to 40,

The number of carbon atoms of the aromatic dicarboxylic acid (C) having 12 or less carbon atoms is 6 to 12,

The polyamide according to any one of (1) to (7), wherein the aliphatic diamine (D) having 12 or less carbon atoms has 6 to 12 carbon atoms.

(9) The content of the unit composed of the aliphatic dicarboxylic acid (A) having 18 or more carbon atoms is 3 to 45 mass% with respect to all monomer components constituting the polyamide,

The content of the unit composed of the aliphatic diamine (B) having 18 or more carbon atoms is 3 to 45% by mass with respect to all monomer components constituting the polyamide,

The content of the unit consisting of the aromatic dicarboxylic acid (C) having 12 or less carbon atoms is 3 to 45 mass% with respect to all monomer components constituting the polyamide,

The poly according to any one of (1) to (9), wherein the content of the unit comprising the aliphatic diamine (D) having 12 or less carbon atoms is 3 to 52% by mass based on all the monomer components constituting the polyamide. amide.

(10) A molded article comprising the polyamide according to any one of (1) to (9).

(11) A film comprising the polyamide according to any one of (1) to (9).

(12) an aliphatic dicarboxylic acid (A) having 18 or more carbon atoms;

An aliphatic diamine (B) having 18 or more carbon atoms;

Reaction product of an aromatic dicarboxylic acid (C) having up to 12 carbon atoms and an aliphatic diamine (D) having up to 12 carbon atoms

A method for producing polyamide by reacting and polymerizing.

(13) C18 or more aliphatic dicarboxylic acid (A) and C18 or more aliphatic diamine (B) are reacted in advance, followed by reaction of C12 or less aromatic dicarboxylic acid (C) with C12 or less aliphatic diamine (D) A method for producing polyamide, wherein a reaction product is reacted and polymerized.

(14) The method for producing a polyamide according to (12) or (13), wherein the polyamide according to any one of (1) to (9) is produced.

According to the present invention, polyamide excellent in all of heat resistance, flexibility, and rubber elasticity can be provided.

Since the polyamide or film of the present invention is formed with a hard segment and a soft segment, it can express excellent flexibility and rubber elasticity.

1A is a diagram showing a hysteresis curve of Example 1;
1B is a diagram showing a hysteresis curve of Example 6;
2 is a diagram showing a hysteresis curve of Comparative Example 1;
3 is a schematic diagram showing a hysteresis curve for explaining a method for calculating a hysteresis loss rate.

The polyamide of the present invention comprises a unit composed of an aliphatic dicarboxylic acid (A) having 18 or more carbon atoms (hereinafter sometimes referred to as component (A)), and an aliphatic diamine (B) having 18 or more carbon atoms (hereinafter, component (B)). (sometimes referred to as), a unit consisting of an aromatic dicarboxylic acid (C) having 12 or less carbon atoms (hereinafter sometimes referred to as component (C)), and an aliphatic diamine (D) having 12 or less carbon atoms ( Hereinafter, it may be referred to as component (D)). Components (A) to (D) are contained as monomer components (or monomer residues) in polyamide. Therefore, "a unit comprising an aliphatic dicarboxylic acid (A) having 18 or more carbon atoms" may simply be expressed as "an aliphatic dicarboxylic acid (A) monomer having 18 or more carbon atoms" or a residue thereof. The "unit comprising an aliphatic diamine (B) having 18 or more carbon atoms" may simply be expressed as "an aliphatic diamine (B) monomer having 18 or more carbon atoms" or a residue thereof. The "unit comprising an aromatic dicarboxylic acid (C) having 12 or less carbon atoms" may simply be expressed as "an aromatic dicarboxylic acid (C) monomer having 12 or less carbon atoms" or a residue thereof. The "unit comprising an aliphatic diamine (D) having 12 or less carbon atoms" may simply be expressed as "an aliphatic diamine (D) monomer having 12 or less carbon atoms" or a residue thereof.

As the aliphatic dicarboxylic acid (A) having 18 or more carbon atoms used in the polyamide of the present invention, an aliphatic dicarboxylic acid composed entirely of hydrocarbons other than the carboxyl group is preferable, and examples thereof include hexadecane dicarboxylic acid (C 18) and octadecane dicarboxylic acid. Carboxylic acid (C 20) and dimer acid (C 36) are exemplified. Among them, aliphatic dicarboxylic acids having 20 or more carbon atoms are preferred, and dimer acids are more preferred, from the viewpoint of increasing flexibility. The dimer acid may be obtained by an addition reaction of two molecules selected from unsaturated fatty acids such as oleic acid and linoleic acid. The two molecules may be molecules of the same kind or molecules of different kinds from each other. The dimer acid may be a dicarboxylic acid having an unsaturated bond, but is preferably a dicarboxylic acid in which all bonds are saturated bonds by hydrogenation because it is difficult to be colored. Component (A) may be used individually by 1 type among the above, or may use 2 or more types together.

The number of carbon atoms in component (A) is preferably 20 to 40, more preferably 30 to 40, from the viewpoint of further improving the heat resistance, flexibility and rubber elasticity of the polyamide and the film containing the polyamide. It is 34 to 38.

The content of component (A) is preferably 3 to 45% by mass, and preferably 5 to 45% by mass, from the viewpoint of further improving the heat resistance, flexibility and rubber elasticity of the polyamide and the film containing the polyamide. More preferably, it is particularly preferable that it is 10 to 45 mass%, and it is more preferable that it is 10 to 40 mass%. The said content is the content of the residue of component (A), and is a ratio with respect to all the monomer components (or the whole quantity of those residues) which comprise a polyamide. When polyamide contains two or more types of components (A), their total amount should just fall within the said range.

As the aliphatic diamine (B) having 18 or more carbon atoms used in the polyamide of the present invention, an aliphatic dicarboxylic acid composed entirely of hydrocarbons except for an amino group is preferable. For example, octadecanediamine (C 18), eicosane diamine ( 20 carbon atoms) and dimer diamine (36 carbon atoms). Especially, dimer diamine is preferable. By using the dimer diamine, the flexibility of the entire polymer can be effectively improved even with a relatively smaller resin composition than other monomers. Usually, dimer diamine is produced by reacting a dimer acid with ammonia, followed by dehydration, nitration, and reduction. The dimer diamine may be a diamine having an unsaturated bond, but is preferably a diamine in which all bonds are saturated bonds by hydrogenation because it is difficult to be colored. Component (B) may be used individually by 1 type among the above, or may use 2 or more types together.

The carbon number of component (B) is preferably 20 to 40, more preferably 30 to 40, from the viewpoint of further improving the heat resistance, flexibility and rubber elasticity of the polyamide and the film containing the polyamide. It is 34 to 38.

The content of component (B) is preferably 3 to 45% by mass, and preferably 5 to 45% by mass, from the viewpoint of further improving the heat resistance, flexibility and rubber elasticity of the polyamide and the film containing the polyamide. More preferably, it is particularly preferable that it is 10 to 45 mass%, and it is more preferable that it is 10 to 40 mass%. The said content is the content of the residue of component (B), and is a ratio with respect to all the monomer components (or the whole amount of those residues) which comprise a polyamide. When polyamide contains two or more types of components (B), their total amount should just fall within the said range.

Examples of the aromatic dicarboxylic acid (C) having 12 or less carbon atoms used in the polyamide of the present invention include terephthalic acid (8 carbon atoms), isophthalic acid (8 carbon atoms), and orthophthalic acid (8 carbon atoms). Among them, aromatic dicarboxylic acids having 8 or more carbon atoms are preferred, and terephthalic acid is more preferred, from the viewpoint of further improving heat resistance, flexibility, and rubber elasticity. Component (C) may be used individually by 1 type among the above, or may use 2 or more types together.

The number of carbon atoms in component (C) is preferably 4 to 12, more preferably 6 to 12, from the viewpoint of further improving the heat resistance, flexibility and rubber elasticity of the polyamide and the film containing the polyamide. It is 6 to 10 at most.

The content of component (C) is preferably 3 to 45% by mass, and preferably 5 to 45% by mass, from the viewpoint of further improving the heat resistance, flexibility and rubber elasticity of the polyamide and the film containing the polyamide. More preferably, it is particularly preferable that it is 5 to 40 mass%, and it is more preferable that it is 8 to 35 mass%. The said content is the content of the residue of component (C), and is a ratio with respect to all the monomer components (or the whole amount of those residues) which comprise a polyamide. When polyamide contains two or more types of components (C), their total amount should just fall within the said range.

As the C12 or less aliphatic diamine (D) used in the polyamide of the present invention, for example, 1,12-dodecanediamine (C12), 1,10-decanediamine (C10), 1 ,9-nonanediamine (carbon number 9), 1,8-octanediamine (carbon number 8), and 1,6-hexanediamine (carbon number 6). Among them, diamines having 6 or more carbon atoms are preferred, diamines having 8 or more carbon atoms are more preferred, and 1,10-decanediamine is still more preferred, from the viewpoint of further improving heat resistance, flexibility, and rubber elasticity. (D) may be used individually by 1 type among the above, or may use 2 or more types together.

The carbon number of component (D) is preferably 4 to 12, more preferably 6 to 12, from the viewpoint of further improving the heat resistance, flexibility and rubber elasticity of the polyamide and the film containing the polyamide. It is 8 to 12 at most.

The content of component (D) is preferably 3 to 52% by mass, and preferably 5 to 50% by mass, from the viewpoint of further improving the heat resistance, flexibility and rubber elasticity of the polyamide and the film containing the polyamide. More preferably, it is particularly preferable that it is 5 to 40 mass%, and it is more preferable that it is 10 to 40 mass%. The said content is the content of the residue of component (D), and is a ratio with respect to all the monomer components (or the whole quantity of those residues) which comprise a polyamide. When polyamide contains two or more types of components (D), their total amount should just fall within the said range.

In the polyamide of the present invention, a unit composed of an aliphatic dicarboxylic acid (A) having 18 or more carbon atoms and a unit composed of an aliphatic diamine (B) having 18 or more carbon atoms form a soft segment, and an aromatic dicarboxylic acid having 12 or less carbon atoms ( It is estimated that the unit consisting of C) and the unit consisting of C12 or less aliphatic diamine (D) form a hard segment. Due to the formation of such a phase-separated structure of the hard segment and the soft segment, it is considered that the polyamide has excellent heat resistance and more sufficiently excellent flexibility and rubber elasticity. In detail, in the polyamide of the present invention, since the hard segment serves as a crosslinking point for rubber and the soft segment can freely expand and contract, flexibility and rubber elasticity (especially rubber elasticity) are expressed while heat resistance is secured. do. Examples of combinations of components (C) and (D) include terephthalic acid and butanediamine, terephthalic acid and 1,9-nonanediamine, terephthalic acid and 1,10-decanediamine, and terephthalic acid and 1,12 -Dodecanediamine is mentioned, and among these, terephthalic acid and 1,10-decanediamine are preferable. By using terephthalic acid and 1,10-decanediamine, since the hard segment tends to become a highly crystalline segment, the formation of a phase-separated structure between the hard segment and the soft segment is promoted, and more sufficiently excellent flexibility and rubber elasticity are expressed. do. "Rubber" is used as a concept of a substance that exhibits the property of being locally deformed by an external force, but returning to its original shape when a force is removed.

The total content of a unit composed of an aliphatic dicarboxylic acid (A) having 18 or more carbon atoms and a unit composed of an aliphatic diamine (B) having 18 or more carbon atoms in the polyamide is the heat resistance, flexibility and From the viewpoint of further improvement of rubber elasticity, it is preferably 10 to 90% by mass, more preferably 15 to 80% by mass, particularly preferably 20 to 80% by mass, and still more preferably 30 to 75% by mass. desirable. The total content is the total amount of residues of component (A) and component (B), and is a ratio to all monomer components constituting polyamide (or the total amount of those residues).

For the polyamide of the present invention, it is preferable not to use a polyether or polyester that is easily decomposed during polymerization. Examples of such a polyether include polyoxyethylene glycol, polyoxypropylene glycol, polyoxytetramethylene glycol, and polyoxyethylene/polyoxypropylene glycol. Examples of polyester include polyethylene adipate, polytetramethylene adipate, and polyethylene sebacate. In the case of using polyether or polyester, if the polymerization temperature is high, decomposition may occur.

The total content of the polyether component and the polyester component is preferably 2% by mass or less, and preferably 1% by mass or less, from the viewpoint of further improving the heat resistance, flexibility and rubber elasticity of the polyamide and the film containing the polyamide. It is more preferable, and it is especially preferable that it is 0.1 mass % or less. The lower limit of the total content range is usually 0% by mass. The total content is the content of the residues of the polyether component and the polyester component, and is a ratio to all monomer components constituting the polyamide (or the total amount of those residues). The polyether component and the polyester component are components constituting a part of the polyamide by covalent bonds with the polyamide, and are not simply blended into the polyamide.

The polyamide of the present invention may contain a terminal blocking agent for the purpose of adjusting the degree of polymerization, suppressing decomposition or discoloration of the product, and the like. Examples of the terminal blocking agent include monocarboxylic acids such as acetic acid, lauric acid, benzoic acid, and stearic acid, and monoamines such as octylamine, cyclohexylamine, aniline, and stearylamine. Terminal blocker may be used individually by 1 type among the above, or may use 2 or more types together. The content of the terminal blocker is not particularly limited, but is usually 0 to 10 mol% with respect to the total molar amount of dicarboxylic acid and diamine.

The polyamide of the present invention may contain additives. Examples of additives include fibrous reinforcing materials such as glass fibers and carbon fibers; fillers such as talc, swellable clay minerals, silica, alumina, glass beads, and graphite; pigments such as titanium oxide and carbon black; antioxidants; antistatic agent; flame retardants; A flame retardant aid is mentioned. Additives may be incorporated during polymerization or may be incorporated by melt kneading or the like after polymerization.

In the polyamide of the present invention, the melting point, which is an indicator of heat resistance, is required to be 240°C or higher, and from the viewpoint of further improving the heat resistance, flexibility and rubber elasticity of the polyamide and the film containing the polyamide, it is 270°C It is preferable that it is above, and it is more preferable that it is 300 degreeC or more. When melting point is too low, heat resistance will fall. The melting point is usually 400°C or less (especially 350°C or less).

In the polyamide of the present invention, the crystal fusion enthalpy, which is an index of crystallinity of the hard segment, is 20 J/g or more from the viewpoint of further improving the heat resistance, flexibility, and rubber elasticity of the polyamide and the film containing the polyamide. It is preferable, it is more preferable that it is 23 J/g or more, and it is more preferable that it is 25 J/g or more. As the crystallinity of the hard segment increases, formation of a phase-separated structure between the hard segment and the soft segment is promoted, and flexibility and rubber elasticity are improved. When the crystal fusion enthalpy is too low, flexibility and/or rubber elasticity decrease. The crystal fusion enthalpy is usually 120 J/g or less (particularly 90 J/g or less).

In particular, the polyamide of the present invention has sufficiently superior flexibility and rubber elasticity than random polyamide described later.

In the polyamide of the present invention, the elongation recovery rate, which is an index of flexibility, is required to be 50% or more, and from the viewpoint of further improving the heat resistance, flexibility and rubber elasticity of the polyamide and the film containing the polyamide, it is 55%. % or more is preferred. When the elongation recovery rate is too low, the flexibility decreases. The elongation recovery rate is usually 100% or less (particularly 90% or less).

The elongation recovery rate of the polyamide of the present invention has the same monomer composition as the polyamide of the present invention, but the conventional polyamide in which the monomer components (components (A) to (D)) are randomly arranged (in this specification, simply random It is more effective to display by contrast with (sometimes referred to as type polyamide). For example, the elongation recovery rate of the polyamide of the present invention is greater than that of the random polyamide. The increase rate (%) of the elongation recovery rate in the polyamide of the present invention is usually 10% or more, preferably 20% or more, and more preferably 40% or more based on the elongation recovery rate of the random polyamide. am. The rate of increase in the elongation recovery rate is usually 300% or less (particularly 200% or less). The increase rate of the elongation recovery rate is expressed as "{(X1-Y1)/Y1} × 100" when the elongation recovery rate of the polyamide of the present invention is represented by X1 and the elongation recovery rate of the random polyamide is represented by Y1. value (%). The random type polyamide is a polyamide obtained by the same method as the method for producing the polyamide of the present invention, except that the raw materials (all monomer components) are put together and polymerized.

In the polyamide of the present invention, the Shore D hardness, which is an index of flexibility, is preferably 75 or less, and more preferably 65 or less. The Shore D hardness is usually 1 or more (especially 2 or more).

Since the Shore D hardness of the polyamide of the present invention also depends on the monomer composition of the polyamide, it is more effective to compare the polyamide of the present invention with a random polyamide having the same monomer composition. For example, the Shore D hardness of the polyamide of the present invention is smaller than the Shore D hardness of the random polyamide. The reduction rate (%) of the Shore D hardness in the polyamide of the present invention is usually 2% or more, preferably 5% or more, and more preferably 6.5% based on the Shore D hardness of the random polyamide. more than % The reduction rate of the Shore D hardness is usually 70% or less (especially 50% or less). The reduction rate of the Shore D hardness is "{(Y2-X2)/Y2}×100" when the Shore D hardness of the polyamide of the present invention is expressed as X2 and the Shore D hardness of the random polyamide is expressed as Y2. is the value (%) represented by

In the polyamide of the present invention, the smaller the hysteresis loss rate, the higher the rubber elasticity. Compared to conventional polyamides in which monomers are randomly polymerized, the polyamide of the present invention has a low hysteresis loss rate because the chain lengths of the hard segments and soft segments in the polymer are controlled. In the polyamide of the present invention, the hysteresis loss rate is preferably 90% or less, more preferably 85% or less, and still more preferably 80% or less. The hysteresis loss rate is usually 10% or more (especially 30% or more).

Since the hysteresis loss rate of the polyamide of the present invention also depends on the monomer composition of the polyamide, it is more effective to compare the polyamide of the present invention with a random polyamide having the same monomer composition. For example, the hysteresis loss rate of the polyamide of the present invention is smaller than that of the random type polyamide. The reduction rate (%) of the hysteresis loss rate in the polyamide of the present invention is usually 2% or more, preferably 4% or more, and more preferably 5.5% or more based on the hysteresis loss rate of the random polyamide. am. The reduction rate of the hysteresis loss rate is usually 40% or less (particularly 30% or less). The rate of decrease of the hysteresis loss rate is expressed as "{(Y3-X3)/Y3} × 100" when the hysteresis loss rate of the polyamide of the present invention is expressed as X3 and the hysteresis loss rate of the random type polyamide is expressed as Y3. value (%).

The polyamide of the present invention can be obtained by reacting component (C) and component (D) separately from components (A) and (B). For example, in the polyamide of the present invention, an aromatic dicarboxylic acid (C) having 12 or less carbon atoms is reacted with an aliphatic diamine (D) having 12 or less carbon atoms to obtain a reaction product, and then the reaction product is aliphatic having 18 or more carbon atoms. It can be obtained by further reacting and polymerizing a dicarboxylic acid (A) and an aliphatic diamine having 18 or more carbon atoms (B). Specifically, the polyamide of the present invention,

component (A); and

component (B);

Reaction product of component (C) and component (D)

It can be obtained by reacting and polymerizing.

In such a manufacturing method, component (A) and component (B) may be used in a state in which they are not reacted with each other, or may be used in a state in which they are reacted with each other (ie, in the form of their reaction products). For example, in the polyamide of the present invention, components (A) and (B) are reacted in advance, and then a reaction product of components (A) and (B) obtained, and components (C) and (D) are formed. You may obtain it by reacting and polymerizing the reaction product of. Specifically, the polyamide of the present invention,

a reaction product of components (A) and (B);

Reaction product of component (C) and component (D)

It may be obtained by reacting and polymerizing.

Component (A) and component (B) are in a state of reacting with each other (ie, in the form of their reaction product) from the viewpoint of further improving the heat resistance, flexibility and rubber elasticity of the polyamide and the film containing the polyamide. It is preferable to use

In the present invention, unlike the conventional polyamide in which components (A) to (D) are randomly polymerized by polymerization as described above, a hard segment composed of components (C) and (D) and component (A) ) and a polyamide composed of a soft segment consisting of (B) is obtained. While the conventional polyamide is a "random polyamide", the polyamide of the present invention can be referred to as a "block polyamide" from the viewpoint of containing a hard segment and a soft segment.

In the production method of the present invention, the reaction obtained by adjusting the monomer ratio [(C)/(D)] of the aromatic dicarboxylic acid (C) having 12 or less carbon atoms and the aliphatic diamine (D) having 12 or less carbon atoms to be used. The chain length of the product can be controlled, and as a result, the flexibility and rubber elasticity of the obtained polyamide can be controlled. From the viewpoint of more sufficiently improving flexibility and rubber elasticity, the molar ratio [(C)/(D)] is preferably 45/55 to 60/40, and more preferably 45/55 to 55/45. .

In the production process of the polyamide of the present invention, a method for producing a reaction product containing an aromatic dicarboxylic acid (C) having 12 or less carbon atoms and an aliphatic diamine (D) having 12 or less carbon atoms (hereinafter simply referred to as "method for producing a reaction product"). (sometimes referred to as "X") is not particularly limited, but is, for example, heated to a temperature higher than the melting point of component (D) and lower than the melting point of component (C) to maintain the powdery state of component (C). To do so, a method of adding component (D) is exemplified. For example, in the case of using terephthalic acid and 1,10-decanediamine as components (C) and (D), respectively, the heating temperature may be 100 to 240°C (especially 140 to 200°C). Addition of component (D) is preferably performed continuously, for example, preferably over 1 to 10 hours (particularly 1 to 5 hours).

The reaction product of component (C) and component (D) may have the form of a salt of component (C) and component (D), or may have the form of a condensate (or oligomer or prepolymer) thereof, or It may have a complex form.

In the case where component (A) and component (B) are reacted in advance, the method for reacting the C18 or more aliphatic dicarboxylic acid (A) with the C18 or more aliphatic diamine (B) is not particularly limited. A method of reacting at a temperature of 150°C (especially 100 to 150°C) for 0.5 to 3 hours is exemplified.

The reaction product of component (A) and component (B), like the reaction product of component (C) and component (D), may also have the form of a salt, and has the form of a condensate (or oligomer or prepolymer) thereof It may exist, or you may have these composite forms.

In the production process of the polyamide of the present invention, the polymerization method is not particularly limited. A method of polymerization at a temperature (preferably a temperature lower than the melting point) is exemplified. Specifically, the hard segment polymer (i.e., polyamide composed only of components (C) and (D) constituting the hard segment) is heated to a temperature below the melting point, and while removing condensation water from the system, the It polymerizes by maintaining temperature. By polymerization in this way, the hard segment is not melted, and only the soft segment can be polymerized in a molten state. Polymerization at a temperature below the melting point of the hard segment polymer is particularly effective in polymerization of polyamide having a high melting point of 280° C. or higher, which tends to decompose due to a high polymerization temperature.

The "melting point of the hard segment polymer" is the melting point of a polyamide formed by sufficiently polymerizing only the components (C) and (D) constituting the hard segment as monomer components. The "melting point of the hard segment polymer" may be, for example, the melting point of a polyamide formed by sufficiently polymerizing only components (C) and (D) as monomer components by the method described in the pamphlet of International Publication No. 2013/042541. In detail, the "melting point of the hard segment polymer" is a polyamide obtained by a method including step (i) of obtaining a reaction product from components (C) and (D) and step (ii) of polymerizing the obtained reaction product. (hard segment polymer). In the process of producing the hard segment polymer, in step (i), components (C) and (D) are heated to a temperature higher than the melting point of component (D) and lower than or equal to the melting point of component (C), ), a reaction product can be obtained by adding component (D) so as to maintain a powdery state. In step (i), for example, when terephthalic acid and 1,10-decanediamine are used as components (C) and (D), respectively, the heating temperature is 100 to 240°C (preferably 140 to 200°C, In particular, 170°C) may be used. It is preferable to add component (D) continuously, for example, over 1 to 10 hours (preferably 1 to 5 hours, particularly 2.5 hours). In the production process of the hard segment polymer, in step (ii), the solid state reaction product obtained in step (i) is sufficiently heated to maintain the solid state, and polymerization (ie, solid phase polymerization) is performed. In step (ii), for example, when terephthalic acid and 1,10-decanediamine are used as components (C) and (D), respectively, the heating temperature (ie, polymerization temperature) is 220 to 300°C (preferably 240 to 280°C, particularly 260°C), and the heating time (that is, polymerization time) may be 1 to 10 hours (preferably 3 to 7 hours, particularly 5 hours). Steps (i) and (ii) are preferably performed in an air stream such as nitrogen inert gas. For example, when terephthalic acid and 1,10-decanediamine are used as components (C) and (D), respectively, the "melting point of the hard segment polymer" is usually 315°C.

Therefore, in producing the polyamide of the present invention, for example, the following method can be employed. First, polymerization is sufficiently performed by the above steps (i) and (ii) using only components (C) and (D) constituting the polyamide to obtain a polyamide (ie, hard segment polymer). Next, the melting point of the obtained polyamide is measured. The measuring method of melting point is not specifically limited, For example, it can measure with a differential scanning calorimeter. Then, after obtaining a reaction product by reacting component (C) with component (D) by the above-described reaction product production method X, the reaction product is heated at a temperature equal to or lower than the "melting point of the hard segment polymer". The polyamide of the present invention can be produced by further reacting and polymerizing with (A) and component (B). In the case of using dimer acid, dimer diamine, terephthalic acid and 1,10-decanediamine as components (A) to (D), respectively, the polymerization temperature is 220 to 300°C (preferably 240 to 280°C, particularly 260°C). ) may be In this case, the polymerization time is not particularly limited as long as sufficient polymerization is performed, and may be, for example, 1 to 10 hours (preferably 3 to 7 hours, particularly 5 hours).

In the manufacturing method of this invention, you may use a catalyst as needed. Examples of the catalyst include phosphoric acid, phosphorous acid, hypophosphorous acid, or salts thereof. The content of the catalyst is not particularly limited, but is usually 0 to 2 mol% with respect to the total molar amount of dicarboxylic acid and diamine.

In the manufacturing method of this invention, you may add an organic solvent or water as needed.

In the production method of the present invention, polymerization may be performed in a closed system or under normal pressure. In the case of performing in a closed system, since the pressure may rise due to volatilization of monomers or generation of condensed water, etc., it is preferable to control the pressure appropriately. On the other hand, when the boiling point of the monomer used is high and the monomer does not flow out of the system even without pressurization, polymerization can be performed under normal pressure. For example, in the case of a combination of dimer acid, dimer diamine, terephthalic acid, and decane diamine, polymerization can be performed under normal pressure.

In the production method of the present invention, in order to prevent oxidative deterioration, it is preferable to perform polymerization under a nitrogen atmosphere or vacuum.

The polymerized polyamide may be extruded into strands to form pellets, or may be hot cut or under water cut into pellets.

In the production method of the present invention, after polymerization, in order to increase the molecular weight, you may further perform solid-state polymerization. Solid state polymerization is particularly effective when the viscosity during polymerization is high and operation becomes difficult. The solid state polymerization is preferably performed by heating at a temperature lower than the melting point of the resin composition for 30 minutes or more, more preferably by heating for 1 hour or more under an inert gas flow or reduced pressure. The melting point of the resin composition may be the same temperature as the "melting point of the hard segment polymer" described above.

The polyamide of the present invention can be formed into a molded article by an injection molding method, an extrusion molding method, a blow molding method, a sinter molding method, or the like. Among them, the injection molding method is preferable in view of the large effect of improving mechanical properties and moldability. Although it does not specifically limit as an injection molding machine, For example, a screw in-line injection molding machine or a plunger type injection molding machine is mentioned. The polyamide heated and melted in the cylinder of the injection molding machine is metered for each shot, injected into the mold in a molten state, cooled and solidified into a predetermined shape, and then taken out of the mold as a molded body. The set temperature of the heater during injection molding is preferably equal to or higher than the melting point.

The molded article of the present invention should just contain the polyamide of the present invention described above, and may further contain other polymers. The content of the polyamide of the present invention in the molded body is usually 50% by mass or more, preferably 70% by mass or more, more preferably 90% by mass or more, and still more preferably 95% by mass relative to the total amount of the molded body. More than that.

When heating and melting the polyamide of the present invention, it is preferable to use sufficiently dried pellets. When the amount of moisture contained in the pellet is high, it may foam in the cylinder of the injection molding machine, making it difficult to obtain an optimal molded article. The moisture content of the pellets used for injection molding is preferably less than 0.3 parts by mass, and more preferably less than 0.1 parts by mass, based on 100 parts by mass of polyamide.

The polyamide of the present invention is used in automobile parts such as fuel tubes, brake piping, intake and exhaust system parts, intake and exhaust system piping, damping materials, and cooling pipes; electrical and electronic components such as pipes, sheets, and connectors; gear; valve; oil pan; cooling fan; radiator tank; cylinder head; canister; hose; soles of sports shoes and the like; medical catheters; bands of wearable devices such as smart watches; protection case; industrial tubing; wire cable; binding band; drone parts; packing; release materials; injection molded articles; Monofilament for 3D printer modeling or fishing line; It can be used for fibers and the like.

The polyamide of the present invention can be particularly suitably used as a film.

The film of the present invention should just contain the polyamide of the present invention described above, and may further contain other polymers. The content of the polyamide of the present invention in the film is usually 50% by mass or more, preferably 70% by mass or more, more preferably 90% by mass or more, and still more preferably 95% by mass with respect to the total amount of the film. More than that.

The film of the present invention is melt-mixed at 240 to 340°C for 3 to 15 minutes, then extruded into a sheet form through a T die, and the extruded product is brought into close contact with a drum temperature controlled at -10 to 80°C for cooling. By doing, an unstretched film can be manufactured. The unstretched film can be further stretched. The obtained unstretched film can be used in an unstretched state, but is usually used as a stretched film in many cases. Stretching is preferably performed in a uniaxial direction or biaxial direction, and more preferably biaxially stretched. Examples of the stretching method include a simultaneous stretching method and a sequential stretching method.

As an example of the simultaneous biaxial stretching method, a method in which an unstretched film is simultaneously biaxially stretched and subsequently subjected to a heat setting treatment is exemplified. Stretching is preferably 1.5 to 5 times in both the width direction (hereinafter sometimes abbreviated as “TD”) and the longitudinal direction (hereinafter sometimes abbreviated as “MD”) at 30 to 150°C. do. The heat setting treatment is preferably performed at 150 to 300° C. for several seconds with a TD relaxation treatment of several percent. Prior to simultaneous biaxial stretching, the film may be preliminarily longitudinally stretched by about 1 to 1.2 times.

As an example of the sequential biaxial stretching method, heat treatment such as roll heating or infrared heating is applied to an unstretched film, followed by stretching in the machine direction, followed by transverse stretching and heat setting treatment. can be heard Longitudinal stretching is preferably performed at 30 to 150°C and 1.5 to 5 times. Transverse stretching is preferably carried out at 30 to 150°C, the same as in the case of longitudinal stretching. As for transverse stretching, it is preferable to make it 1.5 times or more. The heat setting treatment is preferably performed at 150 to 300° C. for several seconds with TD relaxation at several percent.

In the film manufacturing apparatus, processing to reduce surface roughness is performed on the surfaces of cylinders, barrel melting sections, metering sections, single tubes, filters, T-dies, etc. to prevent resin retention. It is desirable to be As a method of reducing surface roughness, a method of modifying with a substance having low polarity is exemplified. Alternatively, a method of depositing silicon nitride or diamond-like carbon on the surface thereof is exemplified.

As a method of extending|stretching a film, a flat type sequential biaxial stretching method, a flat type simultaneous biaxial stretching method, and a tubular method are mentioned, for example. Among them, it is preferable to adopt the flat type simultaneous biaxial stretching method from the viewpoint of improving the thickness accuracy of the film and making the physical properties of the film uniform.

As a stretching apparatus for adopting the flat-type simultaneous biaxial stretching method, a screw-type tenter, a pantograph-type tenter, and a linear motor-driven clip-type tenter are exemplified.

As a heat treatment method after extending|stretching, well-known methods, such as the method of blowing hot air, the method of irradiating infrared rays, and the method of irradiating microwaves, are mentioned, for example. Especially, the method of blowing hot air is preferable at the point which can heat uniformly and with high precision.

The film of the present invention preferably contains a thermal stabilizer in order to enhance thermal stability during film formation, prevent deterioration of strength and elongation of the film, and prevent deterioration of the film due to oxidation or decomposition during use. Examples of the heat stabilizer include hindered phenol-based heat stabilizers, hindered amine-based heat stabilizers, phosphorus-based heat stabilizers, sulfur-based heat stabilizers, and bifunctional heat stabilizers.

Examples of the hindered phenolic heat stabilizer include Irganox 1010 (registered trademark) (manufactured by BASF Japan, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl) propio Nate]), Irganox 1076 (registered trademark) (manufactured by BASF Japan, octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate), Cyanox 1790 (registered trademark) (Solvay Co., Ltd., 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanuric acid), Irganox 1098 (registered trademark) (manufactured by BASF Japan, N,N '-(Hexane-1,6-diyl)bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionamide], Sumilizer GA-80 (registered trademark) (manufactured by Sumitomo Chemical Co., Ltd.) , 3,9-bis[2-{3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy}-1,1-dimethylethyl]-2,4,8,10- tetraoxaspyro[5.5]undecane).

Examples of the hindered amine heat stabilizer include Nylostab S-EED (registered trademark) (manufactured by Clariant Japan, N,N'-bis-2,2,6,6-tetramethyl-4-piperidinyl-1 ,3-benzenedicarboxyamide).

Examples of the phosphorus-based heat stabilizer include Irgafos 168 (registered trademark) (manufactured by BASF Japan, tris (2,4-di-tert-butylphenyl) phosphite), Irgafos 12 (registered trademark) (manufactured by BASF Japan, 6, 6′,6″-[nitrilotris(ethyleneoxy)]tris(2,4,8,10-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphepine)) , Irgafos 38 (registered trademark) (manufactured by BASF Japan, bis(2,4-di-tert-butyl)-6-methylphenyl)ethylphosphite), ADK STAB 329K (registered trademark) (manufactured by ADEKA, tris(mono-dyno) Nylphenyl) phosphite), ADK STAB PEP36 (registered trademark) (manufactured by ADEKA, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol-di-phosphite), Hostanox P-EPQ (registered trademark) trademark) (manufactured by Clariant Corporation, tetrakis (2,4-di-tert-butylphenyl) -4,4'-biphenyldiphosphonite), GSY-P101 (registered trademark) (manufactured by Sakai Chemical Industry, tetrakis ( 2,4-di-tert-butyl-5-methylphenyl)-4,4'-biphenylenediphosphonite), Sumilizer GP (registered trademark) (manufactured by Sumitomo Chemical Co., Ltd., 6-[3-(3-tert) -butyl-4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra-tert-butyldibenzo[d,f][1,3,2]-dioxaphosphepine) can be heard

As the sulfur-based heat stabilizer, for example, DSTP "Yoshitomi" (registered trademark) (manufactured by Mitsubishi Chemical Corporation, chemical name: distearyl thiodipropionate), Seenox 412S (registered trademark) (manufactured by Cipro Chemical Co., Ltd., pentaeryth litol tetrakis-(3-dodecylthiopropionate)).

As a bifunctional heat stabilizer, for example, Sumilizer GM (registered trademark) (manufactured by Sumitomo Chemical Co., Ltd., 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4 -Methylphenyl acrylate), Sumilizer GS (registered trademark) (manufactured by Sumitomo Chemical Co., Ltd., 2-[1-(2-hydroxy-3,5-di-tert-pentylphenyl)ethyl]-4,6-di-tert -pentylphenyl acrylate).

From the viewpoint of preventing deterioration of film strength, a hindered phenolic heat stabilizer is preferable. The thermal decomposition temperature of the hindered phenolic thermal stabilizer is preferably 320°C or higher, and more preferably 350°C or higher. Examples of the hindered phenolic heat stabilizer having a thermal decomposition temperature of 320°C or higher include Sumilizer GA-80. In addition, if the hindered phenol-based heat stabilizer has an amide bond, deterioration of film strength can be prevented. As a hindered phenol type heat stabilizer which has an amide bond, Irganox 1098 is mentioned, for example. Further, deterioration in film strength can be further reduced by using a bifunctional heat stabilizer in combination with the hindered phenol type heat stabilizer.

These thermal stabilizers may be used independently or may use 2 or more types together. For example, when a hindered phenol-based heat stabilizer and a phosphorus-based heat stabilizer are used together, the pressure increase in the filter for filtering raw materials during film formation can be prevented, and deterioration in film strength can be prevented. In addition, when a hindered phenol-based heat stabilizer, a phosphorus-based heat stabilizer, and a bifunctional heat stabilizer are used together, the pressure increase of the filter for filtering the raw material during film formation can be prevented, and the deterioration of the film strength is further reduced. can do.

As a combination of a hindered phenol type heat stabilizer and a phosphorus type heat stabilizer, a combination of Sumilizer GA-80 or Irganox 1098 and Hostanox P-EPQ or GSY-P101 is preferable. As a combination of a hindered phenol-based heat stabilizer, a phosphorus-based heat stabilizer, and a bifunctional heat stabilizer, a combination of Sumilizer GA-80 or Irganox 1098, Hostanox P-EPQ or GSY-P101, and Sumilizer GS is preferable. However, a combination of the smoother GA-80 and GSY-P101 and the smoother GS is more preferable.

The content of the thermal stabilizer in the film of the present invention is preferably 0.01 to 2 parts by mass, more preferably 0.04 to 1 part by mass, based on 100 parts by mass of the polyamide (A). Thermal decomposition can be suppressed more efficiently by making content of a thermal stabilizer into 0.01-2 mass parts. On the other hand, when two or more types of thermal stabilizers are used together, it is preferable that both the individual content of each thermal stabilizer and the total content of the thermal stabilizer fall within the above range.

The film of the present invention may contain lubricant particles in order to improve slipperiness. Examples of the lubricant particles include inorganic particles such as silica, alumina, titanium dioxide, calcium carbonate, kaolin, and barium sulfate, and organic fine particles such as acrylic resin particles, melamine resin particles, silicone resin particles, and crosslinked polystyrene particles. there is.

The film of the present invention may contain various additives as needed within a range not impairing the effects of the present invention. As additives, for example, colorants such as pigments and dyes, anti-coloring agents, antioxidants different from the above thermal stabilizers, weather resistance improving agents, flame retardants, plasticizers, mold release agents, reinforcing agents, modifiers, antistatic agents, ultraviolet absorbers, antifogging agents, various polymers can be heard As a pigment, titanium oxide etc. are mentioned. Examples of the weather resistance improver include benzotriazole-based compounds and the like. Examples of the flame retardant include bromine-based flame retardants and phosphorus-based flame retardants. As a reinforcing agent, talc etc. are mentioned. On the other hand, what is necessary is just to add these various additives at the arbitrary stage at the time of manufacturing a film.

The film of this invention can be treated for improving the adhesiveness of the surface as needed. As a method of improving adhesiveness, corona treatment, plasma treatment, acid treatment, and flame treatment are mentioned, for example.

Various coating agents may be applied to the surface of the film of the present invention in order to impart functions such as easy adhesion, antistatic properties, releasability, and gas barrier properties.

An inorganic substance such as a metal or its oxide, another type of polymer, paper, woven fabric, nonwoven fabric, wood, or the like may be laminated on the stretched film of the present invention.

The film of the present invention has excellent heat resistance, and the melting point, which is an indicator of heat resistance, is required to be 240 ° C. or higher, preferably 250 ° C. or higher, more preferably 270 ° C. or higher, and still more preferably 300 ° C. or higher.

The modulus of elasticity, which is an index of flexibility of the film of the present invention, is preferably 2500 MPa or less, more preferably 2000 MPa or less, and still more preferably 1500 MPa or less.

In addition, the film of the present invention has a low dielectric loss tangent and low permittivity, and excellent dielectric properties, and further excellent insulating properties.

The obtained film may be a single sheet or may be in the form of a film roll by being wound around a winding roll. It is preferable to set it as the form of a film roll from a viewpoint of productivity in use for various uses. In the case of a film roll, it may be slit to a desired width.

The film obtained as described above is excellent in all of heat resistance, flexibility, and rubber elasticity. For this reason, the film of this invention is a packaging material of pharmaceuticals; food packaging materials such as retort foods; packaging materials for electronic components such as semiconductor packages; electrical insulation materials for motors, transformers, cables, wires, multi-layer printed wiring boards, and the like; dielectric materials for capacitor applications and the like; materials for magnetic tapes such as cassette tapes, magnetic tapes for data preservation for digital data storage, and video tapes; protective materials for solar cell substrates, liquid crystal panels, conductive films, glass, digital signage, and other display devices; electronic substrate materials such as LED mounting substrates, organic EL substrates, flexible printed wiring boards, flexible flat cables, flexible antennas, and speaker diaphragms;

heat-resistant protective films such as coverlay films for flexible printed wiring and heat-resistant masking tapes; heat-resistant adhesive films such as heat-resistant barcode labels and various industrial process tapes; heat-resistant reflector; heat-resistant release film; thermal conductive film; Dicing tape, dicing tape-integrated die attach film (dicing/die attach film), dicing tape integrated die bonding film (dicing/die bonding film), dicing tape integrated wafer backside protective film, back grinding film Films for semiconductor processes, such as; materials for molding and decoration such as in-mold molding, film insert molding, vacuum molding, and pressure molding; bonding materials such as interlayer adhesives for laminates and multilayer printed wiring boards, bonding sheets for flexible printed wiring boards, bonding sheets for flexible flat cables, and bonding sheets for coverlay films; shock-absorbing materials such as tube sheathing, wire sheathing, shock-absorbing films, and sealing films; photographic film; agricultural materials; materials for medical use; civil engineering, building materials; household and industrial materials such as filtration membranes; As a film for fiber materials, it can be used suitably. The film of the present invention may be used for the above applications as it is unstretched, or may be stretched and used for the above applications as a stretched film.

Example

Hereinafter, the present invention will be specifically described by examples, but the present invention is not limited thereto.

A. Evaluation method

The physical properties of polyamide and polyamide film were determined by the following methods.

(1) Resin composition

The resulting pellets and powders were subjected to ¹ H-NMR analysis using a high-resolution nuclear magnetic resonance apparatus (ECA-500NMR manufactured by Nippon Electronics Co., Ltd.) to determine the peak intensity of each copolymerization component (resolution: 500 MHz, solvent: heavy water). A mixed solvent with a 4/5 volume ratio of hydrogenated trifluoroacetic acid and deuterated chloroform, temperature: 23°C). In Table 2, the resin composition was expressed as a mass ratio as the final composition.

(2) melting point, crystal fusion enthalpy

Several milligrams were collected from the obtained pellets or powder, and the temperature was raised to 350°C at a heating rate of 20°C/min using a differential scanning calorimeter DSC-7 type (manufactured by PerkinElmer), then maintained at 350°C for 5 minutes, and the temperature was lowered at the rate of cooling. The temperature was lowered to 25°C at 20°C/min, held at 25°C for 5 minutes, and then heated again at a heating rate of 20°C/min.

The top of the heat peak at the time of re-heating was taken as the melting point, and the heat amount of the endothermic peak was taken as the crystal melting enthalpy. Crystal melting enthalpy is obtained from the peak area in the temperature range from the start of melting to the end.

(3) Shore D hardness (flexibility)

After sufficiently drying the obtained pellets or powder, they were molded using an injection molding machine under the conditions of a cylinder temperature of 340 ° C. and a mold temperature of 80 ° C. to produce ISO-compliant general physical property measurement test pieces (dumbbell pieces). It measured based on ASTM D2240 using the obtained test piece.

(4) Elongation recovery rate (flexibility), hysteresis loss rate (rubber elastic modulus)

Dumbbell test pieces were prepared in the same manner as in (3) above, and the elongation recovery rate and hysteresis loss rate were measured using a 2020 type tester manufactured by INTESCO. In a 23 ° C environment, under the conditions of a chuck distance of 55 mm and a tensile test speed of 5 mm / min, it was pulled by 11 mm, immediately returned to its original state at the same speed, and the residual strain A (mm) when the stress was zero was obtained. Hysteresis curves of Examples 1 and 6 and Comparative Example 1 are shown in FIGS. 1A, 1B and 2, respectively.

The elongation recovery rate was calculated by the following formula using the residual strain A.

Kidney recovery rate (%)=(11-A)/11×100

Moreover, it was computed by the following formula from the obtained hysteresis curve.

Hysteresis loss rate (%) = Area (Oabcd) / Area (OabeO) × 100

For example, in FIG. 3 , the area Oabcd is the area of an area indicated by a broken line (vertical broken line), and the area OabeO is the area of an area indicated by a solid line (horizontal solid line). 3 is a schematic diagram showing a hysteresis curve for explaining a method for calculating a hysteresis loss rate.

(5) Tensile breaking strength, tensile elongation at break (flexibility) and tensile modulus of elasticity of the film

According to JIS K 7127, it was measured under an environment of a temperature of 20°C and a humidity of 65%. The size of the sample was 10 mm × 150 mm, the initial distance between chucks was 100 mm, and the tensile speed was 500 mm/min.

(6) Water absorption rate of film

It vacuum-dried at 50 degreeC for 24 hours, measured the weight, and immersed in 23 degreeC pure water. After 24 hours, the moisture on the surface was wiped off, the weight was measured, and the water absorption was determined from the weight change before and after immersion.

(7) Thermal shrinkage rate of film

According to JIS K7133, the shrinkage rate of the film when heat-treated at 200°C for 15 minutes was measured.

(8) dielectric properties of the film

The relative dielectric constant and dielectric loss tangent at 5.8 GHz were measured by the cavity resonator perturbation method. The size of the sample was 2 mm x 50 mm.

B. raw material

The following raw materials were used.

Dimer acid: Prepol 1009 manufactured by Croda

· Terephthalic acid:

Dimer diamine: Preamine 1075 manufactured by Croda

Decanediamine:

Sodium hypophosphite:

· Heat stabilizer: Sumitomo Chemical Co., Ltd. Sumilizer GA-80

Example 1

· Fabrication of reaction products

23.5 parts by mass of terephthalic acid and 0.1 part by mass of sodium hypophosphite monohydrate were introduced into a ribbon blender-type reaction apparatus, and heated at 170°C while stirring at a rotational speed of 30 rpm under nitrogen sealing. After that, 24.4 parts by mass of 1,10-decanediamine heated to 100°C was stirred for 2.5 hours using a liquid pouring device while maintaining the temperature at 170°C and maintaining the rotation speed at 30 rpm. The reaction product was obtained by adding it continuously (continuous liquid pouring method) over the period. On the other hand, the molar ratio of raw material monomers was terephthalic acid:1,10-decanediamine = 50.0:50.0.

· Production of polyamide

26.7 parts by mass of dimer acid and 25.3 parts by mass of dimer diamine were charged into a reaction container equipped with a heating mechanism and a stirring mechanism. After stirring at 100 degreeC for 1 hour, it injected|threw-in stirring 47.9 mass parts of the said reaction product.

Thereafter, the mixture was heated with stirring to 260°C, and polymerization was performed at 260°C under a nitrogen stream at normal pressure for 5 hours while removing condensation water from the system. During polymerization, the system was in the state of a suspension solution.

After polymerization, it was taken out, cut, and dried to obtain polyamide P1 in pellet form.

· Production of film (simultaneous biaxially oriented film)

100 parts by mass of the obtained pellets and 0.4 parts by mass of Smoothizer GA-80 were dry blended, put into a twin-screw extruder with a screw diameter of 26 mm heated to a cylinder temperature of 330 ° C., melt-kneaded, and extruded into a strand shape. After that, it was cooled and cut to obtain pellets.

The obtained pellets were put into a single screw extruder with a screw diameter of 50 mm at the time of heating at a cylinder temperature of 330°C, and melted to obtain a molten polymer. The molten polymer was filtered using a metal fiber sintered filter (Nippon Seisen Co., Ltd., "NF-13", nominal filtration diameter: 60 µm). Then, the molten polymer was extruded into a film form from a T die set at 330°C to obtain a film-like melt. The melt was brought into close contact with a cooling roll set at 0°C by an electrostatic application method and cooled to obtain a substantially non-oriented unstretched polyamide film.

When the resin composition of the polyamide component of the obtained unstretched film was determined, it was the same as the resin composition of the polyamide used.

Biaxial stretching was performed with a flat type simultaneous biaxial stretching machine while holding both ends of the obtained polyamide unstretched film with a clip. The stretching conditions are: the temperature of the preheating part is 80 ° C, the temperature of the stretching part is 80 ° C, the stretching deformation rate of MD is 2400% / min, the stretching deformation rate of TD is 2400% / min, the stretching ratio of MD is 2.3 times, and the TD The draw ratio of was 2.3 times. After stretching, the film was continuously heat-set at 250°C in the same tenter of a biaxial stretching machine, and a 6% relaxation treatment was performed in the width direction of the film to obtain a biaxially stretched polyamide film.

When the resin composition of the polyamide component of the obtained stretched film was determined, it was the same as the resin composition of the polyamide used and the resin composition of the polyamide component of the unstretched film.

Examples 2 to 5

Polyamides P2 to P5 were obtained in the same manner as in Example 1, except that the amount of the monomer charged into the reaction vessel was changed as shown in Table 1. Furthermore, operation similar to Example 1 was performed using the obtained pellet, melt kneading, production of an unstretched film, and simultaneous biaxial stretching were performed to obtain a simultaneous biaxially stretched film.

In the production process of polyamide, the amount of the reaction product added to the reaction vessel was equivalent to the total amount of terephthalic acid and decanediamine used in the production process of the reaction product.

Example 6

· Fabrication of reaction products

26.8 parts by mass of terephthalic acid and 0.1 part by mass of sodium hypophosphite monohydrate were introduced into a ribbon blender-type reaction apparatus, and heated at 170°C while stirring at a rotational speed of 30 rpm under nitrogen sealing. After that, while maintaining the temperature at 170 ° C. and maintaining the rotation speed at 30 rpm, 23.4 parts by mass of 1,10-decanediamine heated to 100 ° C. was continuously added over 2.5 hours using a liquid injection device ( continuous liquid pour method) to obtain a reaction product. On the other hand, the molar ratio of raw material monomers was terephthalic acid:1,10-decanediamine = 54.3:45.7.

· Production of polyamide

18.6 parts by mass of dimer acid and 31.1 parts by mass of dimer diamine were charged into a reaction container equipped with a heating mechanism and a stirring mechanism. After stirring at 100 degreeC for 1 hour, it injected|threw-in stirring 50.2 mass parts of said reaction products.

Thereafter, the mixture was heated with stirring to 260°C, and polymerization was performed at 260°C under a nitrogen stream at normal pressure for 5 hours while removing condensation water from the system. During polymerization, the system was in the state of a suspension solution.

After polymerization, it was taken out, cut, and dried to obtain polyamide P6.

Production of simultaneous biaxially stretched film

Using the obtained pellets, operations similar to those in Example 1 were performed, melt kneading, preparation of an unstretched film, and simultaneous biaxial stretching were performed to obtain a simultaneous biaxially stretched film.

Examples 7 to 9

Polyamides P7 to P9 were obtained in the same manner as in Example 6, except that the amount of the monomer charged into the reaction vessel was changed as shown in Table 1. Furthermore, operation similar to Example 1 was performed using the obtained pellet, melt kneading, production of an unstretched film, and simultaneous biaxial stretching were performed to obtain a simultaneous biaxially stretched film.

In the production process of polyamide, the amount of the reaction product added to the reaction vessel was equivalent to the total amount of terephthalic acid and decanediamine used in the production process of the reaction product.

Example 10

· Fabrication of reaction products

29.7 parts by mass of terephthalic acid and 0.1 part by mass of sodium hypophosphite monohydrate were introduced into a ribbon blender-type reaction apparatus, and heated at 170°C while stirring at a rotational speed of 30 rpm under nitrogen sealing. After that, while maintaining the temperature at 170 ° C. and maintaining the rotation speed at 30 rpm, 20.8 parts by mass of 1,6-hexanediamine heated to 100 ° C. was continuously added over 2.5 hours using a liquid injection device ( continuous liquid pour method) to obtain a reaction product. On the other hand, the molar ratio of raw material monomers was terephthalic acid:1,6-hexanediamine = 50.0:50.0.

· Production of polyamide

25.4 parts by mass of dimer acid and 24.0 parts by mass of dimer diamine were charged into a reaction container equipped with a heating mechanism and a stirring mechanism. After stirring at 100°C for 1 hour, 50.5 parts by mass of the reaction product was introduced while stirring.

Thereafter, the mixture was heated with stirring to 260°C, and polymerization was performed at 260°C under a nitrogen stream at normal pressure for 5 hours while removing condensation water from the system. During polymerization, the system was in the state of a suspension solution.

After the polymerization was completed, it was taken out, cut, and dried to obtain polyamide P10 in pellet form.

Production of simultaneous biaxially stretched film

Using the obtained pellets, operations similar to those in Example 1 were performed, melt kneading, preparation of an unstretched film, and simultaneous biaxial stretching were performed to obtain a simultaneous biaxially stretched film.

Examples 11, 16, 19

· Production of unstretched film

In each of Examples 11, 16 and 19, the substantially non-oriented unstretched polyamide films obtained in Examples 1, 3 and 4 were subjected to heat treatment at 250°C.

Examples 12 to 14

Production of simultaneous biaxially stretched film

A biaxially stretched polyamide film was carried out in the same manner as in Example 1, except that the substantially non-oriented unstretched polyamide film obtained in Example 1 was used and the manufacturing conditions were changed as shown in Table 3. got

Example 17, 18

Production of simultaneous biaxially stretched film

A biaxially stretched polyamide film was carried out in the same manner as in Example 1, except that the substantially non-oriented unstretched polyamide film obtained in Example 3 was used and the manufacturing conditions were changed as shown in Table 3. got

Examples 20, 21

Production of simultaneous biaxially stretched film

A biaxially stretched polyamide film was carried out in the same manner as in Example 1, except that the substantially non-oriented unstretched polyamide film obtained in Example 4 was used and the production conditions were changed as shown in Table 3. got

Example 15 (sequential biaxially oriented film)

The substantially non-oriented unstretched polyamide film obtained in Example 1 was biaxially stretched by a flat-type sequential axial stretching machine. First, the unstretched film was heated to 80° C. by roll heating or infrared heating, and then stretched 3.0 times in MD at a stretching strain rate of 2400%/min to obtain a longitudinally stretched film. Subsequently, transverse stretching was performed by holding both ends of the film in the width direction with clips of a transverse stretching machine continuously. The temperature of the preheating part of the TD stretching was 85 ° C, the temperature of the stretching part was 85 ° C, the stretching deformation rate was 2400% / min, and the stretching ratio of the TD was 3.0 times. Then, in the same tenter of the transverse stretching machine, heat setting was performed at 250°C, and a 6% relaxation treatment was performed in the width direction of the film to obtain a biaxially stretched polyamide film.

Comparative Example 1

In a reaction vessel equipped with a heating mechanism and a stirring mechanism, 26.7 parts by mass of dimer acid, 25.3 parts by mass of dimer diamine, 23.5 parts by mass of terephthalic acid, 24.4 parts by mass of 1,10-decanediamine, and 0.1 part by mass of sodium hypophosphite monohydrate were mixed. put in

Thereafter, while stirring, the mixture was heated to 260°C, and polymerization was performed at 260°C under a nitrogen stream at normal pressure for 5 hours while removing condensation water from the system. During polymerization, the system was in a suspended state.

After polymerization, it was taken out, cut, and dried to obtain polyamide P11 in pellet form.

Furthermore, operation similar to Example 1 was performed using the obtained pellet, melt kneading, production of an unstretched film, and simultaneous biaxial stretching were performed to obtain a simultaneous biaxially stretched film.

Comparative Examples 2 to 5

Polyamides P12 to 15 were obtained in the same manner as in Comparative Example 1, except that the amounts of dimer acid, dimer diamine, terephthalic acid, and 1,10-decanediamine were changed to the amounts shown in Table 1.

Furthermore, operation similar to Example 1 was performed using the obtained pellet, melt kneading, production of an unstretched film, and simultaneous biaxial stretching were performed to obtain a simultaneous biaxially stretched film.

Comparative Example 6

49.0 parts by mass of terephthalic acid and 0.1 part by mass of sodium hypophosphite monohydrate were charged into a powder stirring device equipped with a heating mechanism. While stirring under heating at 170°C, 50.9 parts by mass of 1,10-decanediamine was added little by little over 3 hours to obtain a reaction product. Thereafter, while stirring, the reaction product was heated to 250°C, and polymerization was performed at 250°C under a nitrogen stream at normal pressure for 7 hours while condensation water was removed from the system. During polymerization, the system was in a powder state.

After polymerization, it was taken out to obtain polyamide P16 in powder form.

Furthermore, operation similar to Example 1 was performed using the obtained powder, melt kneading, production of an unstretched film, and simultaneous biaxial stretching were performed to obtain a simultaneous biaxially stretched film.

Comparative Example 7

51.3 parts by mass of dimer acid, 48.6 parts by mass of dimer diamine, and 0.1 part by mass of sodium hypophosphite monohydrate were charged into a reaction container equipped with a heating mechanism and a stirring mechanism.

Thereafter, while stirring, the mixture was heated to 260°C, and polymerization was performed for 5 hours at 260°C under a nitrogen stream at normal pressure while removing condensation water from the system. During polymerization, the system was in a uniform molten state.

After the polymerization was completed, it was taken out, cut, and dried to obtain polyamide P17 in the form of pellets.

Moreover, melt-kneading, preparation of an unstretched film, and simultaneous biaxial stretching were performed by performing the same operation as in Example 1 using the obtained pellet, but a stretched film could not be obtained.

Comparative Example 8

In a reaction vessel equipped with a heating mechanism and a stirring mechanism, 51.0 parts by mass of polyoxytetramethylene glycol (PTMG1000) having a number average molecular weight of 1000 having amino groups instead of hydroxyl groups at both ends, 28.3 parts by mass of terephthalic acid, and 1,10-decane 20.6 parts by mass of canediamine and 0.1 part by mass of sodium hypophosphite monohydrate were charged.

Then, while stirring, it heated to 250 degreeC, and superposition|polymerization was performed for 5 hours at 250 degreeC under a nitrogen stream and normal pressure, removing condensation water out of the system. During polymerization, the system was in the state of a suspension solution.

After the polymerization was completed, it was taken out, cut, and dried to obtain polyamide P18 in the form of pellets, but it was brittle and was not suitable for practical use.

Comparative Examples 9, 11, 13

· Production of unstretched film

In each of Comparative Examples 9, 11, and 13, the substantially non-oriented unstretched polyamide films obtained in Comparative Examples 1, 3, and 4 were subjected to heat treatment at 200°C.

Comparative Examples 10, 12, 14

In each of Comparative Examples 10, 12, and 14, except for using the substantially non-oriented unstretched polyamide films obtained in Comparative Examples 1, 3, and 4 and changing the manufacturing conditions as shown in Table 3, The same operation as in Example 1 was performed to obtain a biaxially stretched polyamide film.

Table 1 shows the charged composition of the polyamides obtained in Examples 1 to 10 and Comparative Examples 1 to 8, the molar ratio of components (C) and (D), and the polymerization method.

The symbol in Table 1 is as follows.

A = fatty acid dicarboxylic acid (A) having at least 18 carbon atoms (dimer acid)

C = Aromatic dicarboxylic acid (C) having up to 12 carbon atoms (terephthalic acid)

B = aliphatic diamine having 18 or more carbon atoms (B) (dimer diamine)

D1 = aliphatic diamine having 12 or less carbon atoms (D) (decanediamine)

D2 = aliphatic diamine having 12 or less carbon atoms (D) (1,6-hexanediamine)

E = PTMG1000 with amino groups at both ends

F = sodium hypophosphorous acid monohydrate

Table 2 shows the final composition of the polyamides obtained in Examples 1 to 10 and Comparative Examples 1 to 8, the obtained polyamides, and evaluation of the obtained biaxially stretched films.

The symbol in Table 2 is as follows.

A to C, D1, D2 and E, respectively, are the same as A to C, D1, D2 and E in Table 1.

(1) reduction rate (%) of Shore D hardness;

(2) increase in renal recovery rate (%);

(3) Decrease rate (%) of hysteresis loss rate.

In Table 2, the value of (1) to (3) is shown only in Examples 1 to 5 because Comparative Examples 1 to 5 having the same monomer composition as each of Examples 1 to 5 exist. It is significant to compare the values in Examples and Comparative Examples of the same monomer composition with each other.

The reduction rate (%) of the Shore D hardness in Examples 1 to 5 is the ratio of the decrease from the Shore D hardness in Comparative Examples 1 to 5, respectively.

The reduction rate of the Shore D hardness is usually 2% or more (Δ: range without problems in practical use), preferably 5% or more (○: good), and more preferably 6.5% or more (◎: excellent).

The increase rate (%) of the elongation recovery rate in Examples 1 to 5 is the ratio of the increase from the elongation recovery rate in Comparative Examples 1 to 5, respectively.

The rate of increase in the elongation recovery rate is usually 10% or more (Δ: no problem in practical use), preferably 20% or more (○: good), and more preferably 40% or more (◎: excellent).

The reduction rate (%) of the hysteresis loss rate in Examples 1 to 5 is the ratio of the decrease from the hysteresis loss rate in Comparative Examples 1 to 5, respectively.

The rate of reduction of the hysteresis loss rate is usually 2% or more (Δ: range without problems in practical use), preferably 4% or more (○: good), and more preferably 5.5% or more (◎: excellent).

In Examples 1 to 5, the melting point is usually 240 ° C. or higher (Δ: range without problems in practical use), preferably 270 ° C. or higher (○: good), more preferably 300 ° C. or higher (◎: excellent )am.

In Examples 1 to 5, for all evaluation results of melting point, reduction rate (%) of Shore D hardness, increase rate (%) of elongation recovery rate, and reduction rate (%) of hysteresis loss rate, the more evaluation items giving ◎, the more preferable it is. do.

Table 3 shows evaluation of the unstretched films obtained in Examples 11, 16 and 19 and evaluation of the biaxially stretched films obtained in Examples 12 to 15, 17, 18, 20 and 21.

For Examples 11, 1, 3, and 4 and Comparative Examples 9, 1, 3, 4, and 6, the 200°C heat shrinkage rate and the evaluation of dielectric properties (relative permittivity and dielectric loss tangent) are shown in Table 4.

Since the polyamides of Examples 1 to 10 satisfied the requirements stipulated in the present invention, all of them had a melting point of 240°C or higher, which is an indicator of heat resistance, and an elongation recovery rate of 50% or more in a hysteresis test, which is an indicator of flexibility. It has excellent heat resistance and flexibility. In addition, since the polyamides of Examples 1 to 10 had crystal fusion enthalpy, which is an index of crystallinity of the hard segment, 20 J/g or more, the hard segment could sufficiently serve as a crosslinking point and had excellent rubber elasticity. The obtained stretched film was also excellent in flexibility.

The polyamides of Examples 1 to 5 and the polyamides of Comparative Examples 1 to 5 were prepared by a two-step method in which a reaction product of the hard segment was prepared and then added to the reaction product of the soft segment for polymerization. Polyamide has a higher elongation recovery rate and enthalpy of crystal fusion than polyamide obtained by a conventional one-step method in which the raw materials are integrated and introduced and polymerized, and the Shore D hardness and hysteresis loss rate are small, and flexibility and rubber elasticity are improved. it can be seen that there is Elongation improved also about the obtained stretched film, and the elastic modulus was also falling.

The polyamides of Comparative Examples 1 and 3 to 5 had low elongation recovery rates and low flexibility.

The polyamide of Comparative Example 2 had a low crystal fusion enthalpy and low crystallinity of the hard segment.

Since the polyamide of Comparative Example 6 did not have the components (A) and (B) forming the soft segment, the elongation recovery rate was low and the flexibility was low.

Since the polyamide of Comparative Example 7 did not have components (C) and (D) forming a hard segment, it had no melting point and had low heat resistance.

Since the polyamide and film of the present invention are excellent in all properties of heat resistance, flexibility and rubber elasticity, they are useful for all kinds of applications requiring these properties, such as packaging materials.

Claims (14)

A unit composed of an aliphatic dicarboxylic acid (A) having 18 or more carbon atoms, a unit composed of an aliphatic diamine (B) having 18 or more carbon atoms, a unit composed of an aromatic dicarboxylic acid (C) having 12 or less carbon atoms, and an aliphatic diamine having 12 or less carbon atoms A polyamide containing a unit comprising (D) and having a melting point of 240°C or higher, a crystal fusion enthalpy of 20 J/g or higher, and an elongation recovery rate of 50% or higher in a hysteresis test. According to claim 1,
Polyamide, wherein the aliphatic dicarboxylic acid (A) having 18 or more carbon atoms is a dimer acid. According to claim 1 or 2,
Polyamide, wherein the aliphatic diamine (B) having 18 or more carbon atoms is a dimer diamine. According to any one of claims 1 to 3,
Polyamide, wherein the aromatic dicarboxylic acid (C) having 12 or less carbon atoms is terephthalic acid. According to any one of claims 1 to 4,
Polyamide, wherein the aliphatic diamine (D) having 12 or less carbon atoms is 1,10-decanediamine. According to any one of claims 1 to 5,
The total content of the unit composed of the aliphatic dicarboxylic acid (A) having 18 or more carbon atoms and the unit composed of the aliphatic diamine (B) having 18 or more carbon atoms is 10 to 90 mass, based on all the monomer components constituting the polyamide. % phosphorus, polyamide. According to any one of claims 1 to 6,
The total content of the unit composed of the aliphatic dicarboxylic acid (A) having 18 or more carbon atoms and the unit composed of the aliphatic diamine (B) having 18 or more carbon atoms is 20 to 80 mass based on all the monomer components constituting the polyamide. % phosphorus, polyamide. According to any one of claims 1 to 7,
The number of carbon atoms of the aliphatic dicarboxylic acid (A) having 18 or more carbon atoms is 30 to 40,
The number of carbon atoms of the aliphatic diamine (B) having 18 or more carbon atoms is 30 to 40,
The number of carbon atoms of the aromatic dicarboxylic acid (C) having 12 or less carbon atoms is 6 to 12,
A polyamide having 6 to 12 carbon atoms of the aliphatic diamine (D) having 12 or less carbon atoms. According to any one of claims 1 to 8,
The content of the unit composed of the aliphatic dicarboxylic acid (A) having 18 or more carbon atoms is 3 to 45% by mass with respect to all monomer components constituting the polyamide,
The content of the unit composed of the aliphatic diamine (B) having 18 or more carbon atoms is 3 to 45% by mass with respect to all monomer components constituting the polyamide,
The content of the unit consisting of the aromatic dicarboxylic acid (C) having 12 or less carbon atoms is 3 to 45 mass% with respect to all monomer components constituting the polyamide,
The polyamide, wherein the content of the unit composed of the aliphatic diamine (D) having 12 or less carbon atoms is 3 to 52% by mass with respect to all monomer components constituting the polyamide. A molded article comprising the polyamide according to any one of claims 1 to 9. A film comprising the polyamide according to any one of claims 1 to 9. An aliphatic dicarboxylic acid (A) having 18 or more carbon atoms;
An aliphatic diamine (B) having 18 or more carbon atoms;
Reaction product of an aromatic dicarboxylic acid (C) having up to 12 carbon atoms and an aliphatic diamine (D) having up to 12 carbon atoms
A method for producing polyamide by reacting and polymerizing. After preliminarily reacting an aliphatic dicarboxylic acid (A) having 18 or more carbon atoms with an aliphatic diamine (B) having 18 or more carbon atoms, a reaction product of an aromatic dicarboxylic acid (C) having 12 or less carbon atoms and an aliphatic diamine (D) having 12 or less carbon atoms is prepared. A method for producing polyamide by reacting and polymerizing. According to claim 12 or 13,
A method for producing a polyamide, wherein the polyamide according to any one of claims 1 to 9 is produced.

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